CN112851449A - Fluorine-containing polymer coated high-purity boron powder and preparation method thereof - Google Patents

Fluorine-containing polymer coated high-purity boron powder and preparation method thereof Download PDF

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Publication number
CN112851449A
CN112851449A CN202110094742.5A CN202110094742A CN112851449A CN 112851449 A CN112851449 A CN 112851449A CN 202110094742 A CN202110094742 A CN 202110094742A CN 112851449 A CN112851449 A CN 112851449A
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Prior art keywords
boron powder
fluorine
containing polymer
purity boron
fluoropolymer
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CN202110094742.5A
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Inventor
王贵宗
翟一鸣
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Jiangsu Zhiren Jingxing New Material Research Institute Co ltd
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Jiangsu Zhiren Jingxing New Material Research Institute Co ltd
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Priority to CN202110094742.5A priority Critical patent/CN112851449A/en
Publication of CN112851449A publication Critical patent/CN112851449A/en
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0008—Compounding the ingredient
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
    • C06B45/30—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component
    • C06B45/32—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component the coating containing an organic compound
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Glanulating (AREA)

Abstract

The invention discloses a fluorine-containing polymer coated high-purity boron powder, which is coated by adopting a fluorine-containing polymer, not only can reduce the specific surface free energy of boron powder particles and reduce the agglomeration phenomenon, but also can obviously improve the combustion efficiency of the boron powder, and provides a preparation method of the fluorine-containing polymer coated high-purity boron powder. The fluoropolymer-coated high-purity boron powder obtained by the method can well solve the problems that the combustion efficiency is low in the amorphous boron powder re-solid propellant, and the heat value of the boron powder cannot be effectively exerted. The coating preparation process introduced by the invention is simple, the coating process is high in engineering realizability, and the economic added value is high.

Description

Fluorine-containing polymer coated high-purity boron powder and preparation method thereof
Technical Field
The invention belongs to the field of energetic materials, and particularly relates to fluoropolymer-coated high-purity boron powder for a solid propellant and a preparation method thereof.
Background
Boron powder is an energetic material with a high combustion heat value and is widely used in solid propellants and explosives. Boron powder generates boron oxide (B) with low melting point in the combustion process2O3) The amorphous boron powder has a high melting point and is not easy to melt and vaporize, so that the combustion efficiency is low, and the high combustion heat value cannot be effectively exerted.
In order to improve the combustion efficiency of boron powder, a great deal of technical research is carried out at home and abroad. In the aspect of technology for solving the combustion efficiency of boron powder, the technology of compounding, granulating, coating and the like is adopted in China. At present, boron powder coating technologies such as LiF coating technology, azide polymer coating technology, butylated hydroxytoluene coating technology and the like are adopted in many cases. The problem of poor process performance of LiF coated boron powder in an HTPB system can occur; the azide polymer is easy to coat unevenly, so that the viscosity of the system is increased. Besides, in the aspect of improving the combustion of boron powder, the method of granulating compound AP and coating the compound AP by using a fluorine-containing material is also researched in China, the essence of AP compounding is that an oxidant is used for improving the combustion efficiency of the AP, and the fluorine-containing material coating is that B and F are expected to have chemical reaction to generate BF3So that the combustion reaction of the internal boron powder can be continuously carried out in the combustion process.
The research of improving the combustion efficiency of the boron-containing propellant by adding magnesium and aluminum metal powder is reported abroad, the combustion efficiency of the boron-containing propellant added with magnesium powder is greatly improved, and the pressure index of the propellant is improved. Although these methods improve the combustion efficiency of amorphous boron powder to a greater or lesser extent, the combination of process properties and combustion properties has not met the specifications for commercial applications. Therefore, there is an urgent need to develop a new method for improving the combustion efficiency of boron powder.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-purity boron powder coated with a fluorine-containing polymer, wherein the fluorine-containing polymer is used for coating the high-purity boron powder, so that the specific surface free energy of boron powder particles can be reduced, the agglomeration phenomenon is reduced, the combustion efficiency of the boron powder can be obviously improved, and the preparation method of the high-purity boron powder coated with the fluorine-containing polymer is provided.
In order to achieve the purpose, the invention adopts the following technical scheme: the fluoropolymer-coated high-purity boron powder is characterized in that the surface of the high-purity boron powder is coated with a layer of fluoropolymer, wherein the fluoropolymer accounts for 2-20% of the total mass.
Further, the fluorine-containing polymer is polytetrafluoroethylene, a copolymer of vinylidene fluoride and chlorotrifluoroethylene, a copolymer of vinylidene fluoride and hexafluoropropylene, a terpolymer of vinylidene fluoride, chlorotrifluoroethylene and hexafluoropropylene, or a derivative of the above-mentioned fluorine-containing polymer.
Furthermore, the average grain diameter of the high-purity boron powder is 1-3 mu m, and the boron content is 92-95%.
The preparation method of the fluorine-containing polymer coated high-purity boron powder comprises the following steps:
(1) preparing a fluorine-containing polymer coating solution, adding high-purity boron powder into the fluorine-containing polymer coating solution, and coating a layer of fluorine-containing polymer on the surface of the high-purity boron powder under the condition of high-speed stirring;
(2) carrying out post-treatment on the reacted solution to obtain a crude product filter cake;
(3) and drying and dispersing the crude product filter cake to obtain the fluoropolymer-coated high-purity boron powder.
Further, the fluoropolymer coating solution is prepared by dissolving the fluoropolymer in a coating solution, wherein the coating solution is one or a mixed solvent of two of ethanol, acetone, ethyl acetate, chloroform, dichloromethane and DMF. More preferably, acetone or ethyl acetate solvents are employed.
Further, the mass ratio of the fluoropolymer coating solution to the high-purity boron powder in the step (1) is 2: 1-5: 1.
Further, the reaction conditions of the coating process in the step (1) are as follows: the reaction time is 1-5 h, the preferable time is 2h, the heating temperature is 40-60 ℃, the reaction is naturally cooled after the reaction is finished, and the stirring speed is reduced to 200-300 r/min.
Further, the post-treatment in the step (2) adopts a rotary evaporator to evaporate the solvent by vacuumizing or adopts a centrifugal device to centrifugally separate the organic solvent.
Further, in the drying in the step (3), heating and drying are carried out in a vacuum drying oven, the heating temperature is 80-130 ℃, and the vacuumizing and drying time is 2-7 hours. The preferable heating temperature is 100-110 ℃, and the preferable heating temperature is 3-4 h.
Further, in the step (3), ultrasonic dispersion is carried out on the ultrasonic device again, wherein the ultrasonic time is 20-50 min, and the frequency is 40-60 kHz.
The high-purity boron powder coated by the fluoropolymer is a functional material for a solid propellant, can be well compatible with other components of the propellant, and can remarkably improve the combustion efficiency of the boron powder, so that the combustion performance of the boron-containing propellant is improved.
And vibrating and sieving the product subjected to ultrasonic treatment, and packaging and detecting the product in grades.
The fluoropolymer-coated high-purity boron powder detection items comprise: moisture, particle size, density, heat of combustion, etc.
The invention does not report about the fluoropolymer coated high-purity boron powder and the process technology thereof. The fluoropolymer-coated high-purity boron powder obtained by the method can well solve the problems that the combustion efficiency is low in the amorphous boron powder re-solid propellant, and the heat value of the boron powder cannot be effectively exerted. The coating preparation process introduced by the invention is simple, the coating process is high in engineering realizability, and the economic added value is high.
Detailed Description
In order to make the technical solutions of the present application better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that the terms "comprises" and "comprising," and any variations thereof, in the description and claims of this application, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
The embodiment provides high-purity boron powder coated by a vinylidene fluoride and hexafluoropropylene copolymer derivative and a preparation method thereof.
Selecting self-made high-purity boron powder with the average particle size of 1 mu m and the boron content of 95 percent; the coating agent is selected from commercially available vinylidene fluoride and hexafluoropropylene copolymers.
The coating process comprises the following steps: a certain amount of vinylidene fluoride and hexafluoropropylene copolymer was dissolved in 1000mL of ethyl acetate (Table 1), and the fluoropolymer was heated in the solvent at 40 ℃ under stirring for 1 hour until the fluoropolymer was completely dissolved, to prepare a fluoropolymer-coated solution. Then, it was transferred to a glass vessel equipped with a mechanical stirring device, and 400g of high purity boron powder was poured therein and stirred to react for 3 hours. The suspension was then poured into a rotary evaporator, heated to 50 ℃ and the ethyl acetate removed. The brown slurry was then spread on a tray and dried under vacuum for 3 hours.
TABLE 1 fluoropolymer coating ratio and raw material amounts
Fluoropolymer coating ratio Amount of coating agent High-purity boron powder Ethyl acetate
1％ 10g 400g 1000mL
2％ 20g 400g 1000mL
3％ 30g 400g 1000mL
And (3) placing the boron powder coated by the fluorine-containing polymer in an ultrasonic device, and performing ultrasonic dispersion for 30min at the frequency of 40 kHz. And then filtering the dispersed product by using a 300-mesh sieve, collecting the product and packaging.
Taking a part of samples for test analysis, and respectively measuring the moisture content to be 0.105%, 0.093% and 0.091%; the particle size is as follows: 25.5 μm, 19.8 μm, 33.6. mu.m.
Example 2
The embodiment provides high-purity boron powder coated by a terpolymer derivative of vinylidene fluoride/chlorotrifluoroethylene/hexafluoropropylene and a preparation method thereof.
Selecting self-made high-purity boron powder with the average particle size of 1 mu m and the boron content of 95 percent; the coating agent is selected from the commercial terpolymer of vinylidene fluoride/chlorotrifluoroethylene/hexafluoropropylene containing terminal carboxyl groups.
The coating process comprises the following steps: a certain amount of vinylidene fluoride/chlorotrifluoroethylene/hexafluoropropylene terpolymer was dissolved in 2000mL of acetone (Table 2), and the fluoropolymer was heated in the solvent at 50 ℃ with stirring for 1 hour until the fluoropolymer was completely dissolved, to prepare a fluoropolymer-coated solution. Then, it was transferred to a glass vessel equipped with a mechanical stirring device, and 600g of high purity boron powder was poured therein, and the reaction was stirred for 2 hours. The suspension was then poured into a rotary evaporator, heated to 50 ℃ and the ethyl acetate removed. The brown slurry was then spread on a tray and dried under vacuum for 4 hours.
TABLE 2 fluoropolymer coating ratio and raw material amounts
Fluoropolymer coating ratio Amount of coating agent High-purity boron powder Ethyl acetate
1％ 20g 600g 2000mL
2％ 40g 600g 2000mL
3％ 60g 600g 2000mL
And (3) placing the boron powder coated by the fluorine-containing polymer in an ultrasonic device, and performing ultrasonic dispersion for 50min at the frequency of 60 kHz. And then filtering the dispersed product by using a 500-mesh sieve, collecting the product and packaging.
Taking a part of samples for test analysis, and respectively measuring the moisture content to be 0.085%, 0.088% and 0.095%; the particle size is as follows: 17.2 μm, 22.1 μm, 14.6. mu.m.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (10)

1. A fluorine-containing polymer coated high-purity boron powder is characterized in that: the surface of the high-purity boron powder is coated with a layer of fluorine-containing polymer, wherein the fluorine-containing polymer accounts for 2-20% of the total mass.
2. The fluoropolymer-coated high purity boron powder of claim 1, wherein: the fluorine-containing polymer is polytetrafluoroethylene, a copolymer of vinylidene fluoride and chlorotrifluoroethylene, a copolymer of vinylidene fluoride and hexafluoropropylene, a terpolymer of vinylidene fluoride, chlorotrifluoroethylene and hexafluoropropylene, or a derivative of the fluorine-containing polymer.
3. The fluoropolymer-coated high purity boron powder of claim 1, wherein: the average grain size of the high-purity boron powder is 1-3 mu m, and the boron content is 92-95%.
4. A method for preparing a fluorine-containing polymer-coated high purity boron powder according to any one of claims 1 to 3, characterized by comprising the steps of:
(1) preparing a fluorine-containing polymer coating solution, adding high-purity boron powder into the fluorine-containing polymer coating solution, and coating a layer of fluorine-containing polymer on the surface of the high-purity boron powder under the condition of high-speed stirring;
(2) carrying out post-treatment on the reacted solution to obtain a crude product filter cake;
(3) and drying and dispersing the crude product filter cake to obtain the fluoropolymer-coated high-purity boron powder.
5. The method of claim 4, wherein: the preparation method of the fluorine-containing polymer coating solution comprises the step of dissolving a fluorine-containing polymer in a coating solution, wherein the coating solution is one or a mixed solvent of two of ethanol, acetone, ethyl acetate, chloroform, dichloromethane and DMF.
6. The method of claim 4, wherein: the mass ratio of the fluoropolymer coating solution to the high-purity boron powder in the step (1) is 2: 1-5: 1.
7. The method of claim 4, wherein: the reaction conditions of the coating process in the step (1) are as follows: the reaction time is 1-5 h, the heating temperature is 40-60 ℃, the temperature is naturally reduced after the reaction is finished, and the stirring speed is reduced to 200-300 r/min.
8. The method of claim 4, wherein: and (3) carrying out post-treatment in the step (2) by adopting a rotary evaporator to evaporate the solvent by vacuumizing or adopting a centrifugal device to carry out centrifugal separation on the organic solvent.
9. The method of claim 4, wherein: and (3) heating and drying in a vacuum drying oven at the heating temperature of 80-130 ℃ for 2-7 h.
10. The method of claim 4, wherein: and (3) carrying out ultrasonic dispersion on the ultrasonic in the ultrasonic step, wherein the ultrasonic time is 20-50 min, and the frequency is 40-60 kHz.
CN202110094742.5A 2021-01-25 2021-01-25 Fluorine-containing polymer coated high-purity boron powder and preparation method thereof Pending CN112851449A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008042446A2 (en) * 2006-10-07 2008-04-10 Momentive Performance Materials, Inc. Mixed boron nitride composition and method for making thereof
CN101759508A (en) * 2010-01-07 2010-06-30 同济大学 Method for increasing combustion efficiency of boron powder

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008042446A2 (en) * 2006-10-07 2008-04-10 Momentive Performance Materials, Inc. Mixed boron nitride composition and method for making thereof
CN101759508A (en) * 2010-01-07 2010-06-30 同济大学 Method for increasing combustion efficiency of boron powder

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